The photophysical properties of a number of ruthenium complexes of the general structure {Ru(L1)(L2)-(NCS)(2)], related to the prominent solar cell dye [Ru(dcb)(2)(NCS)(2)] (dcb = 4,4'-dicarboxylato-2,2'-bipyridine) are investigated. For L1 = dcb and dmb (dmb = 4,4'-dimethyl-2,2'-bipyridine), several variations of L2 show very little difference in the lowest energy absorption peak. Resonance Raman and density functional theory calculations have been used to assign the corresponding transitions as {Ru(NCS)(2)} -> dcb with significant contributions of the NCS ligands. Transient absorption, time-resolved infrared, and transient resonance Raman spectroscopic techniques were used to probe the photophysics of the complexes and relatively shortlived {Ru(NCS)(2)} > dcb/dpb (dpb = 4,4'-diphenylethenyl-2,2'-bipyridine) excited states were observed with the exception of [Ru(dcb)(dab)(NCS)(2)] (dab = 4,4'-dianthracenethenyl-2,2'-bipyridine), which showed a long-lived excited state assigned as ligand centered charge separated.